Türkmen, Y. E.Gravel, M.Rawal, V. H.2018-04-122018-04-1220160022-3263http://hdl.handle.net/11693/36744We have developed an efficient route for the synthesis of the perhydroquinoline core of the indole alkaloid aspidophytine (2), starting from commercially available and inexpensive 3-acetylpyridine. This densely functionalized perhydroquinoline core displays four contiguous stereocenters including an all-carbon quaternary center. The synthetic sequence features a highly effective Diels-Alder reaction using a carbamate-substituted siloxy diene accompanied by a spontaneous intramolecular substitution of the newly formed 3°-alkyl bromide with a carbamate group. The installation of the electron-rich aniline moiety was accomplished via a TBSOTf-mediated intramolecular aza-Michael reaction, and the relative stereochemistry of the aza-Michael product (30) was confirmed by X-ray crystallographic analysis. Among the useful transformations that were developed through this study is a highly enantioselective Diels-Alder reaction of a versatile cyclic carbamate siloxy diene.EnglishAddition reactionsCarbonEnantioselectivityIonic liquidsOlefinsX ray crystallographyAza-Michael reactionContiguous stereocentersDiels-Alder reactionEnantioselective Diels-Alder reactionsIntramolecular substitutionsQuaternary centersSynthetic sequenceX-ray crystallographic analysisChemical reactionsArticle10.1021/acs.joc.6b015741520-6904